ethyl 4-diazo-2,2-dimethyl-3-oxobutyrate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 4-diazo-2,2-dimethyl-3-oxobutyrate
• 英文别名: Ethyl 4-diazo-2,2-dimethyl-3-oxobutanoate；ethyl 4-diazo-2,2-dimethyl-3-oxobutanoate
• 化学式: C₈H₁₂N₂O₃
• 分子量: 184.195
• InChiKey: CHUVYWUUBOTJGD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  45.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 4-diazo-2,2-dimethyl-3-oxobutyrate 在 三氟化硼乙醚 作用下， 以 甲醇 为溶剂， 反应 0.25h， 以90%的产率得到3,3-二甲基呋喃-2,4(3H,5H)-二酮
  参考文献：
  名称：

  酸催化重氮酮的环化反应：制备2,4（3H，5H）呋喃二酮

  摘要：

  通过在甲醇中催化量的三氟化硼醚化物的存在下，由相应的丙二酸酯的选择性水解产生的由取代的丙二酸氢乙酯生成的重氮酮环化，生成2,4（3H，5H）呋喃二酮。环状酮基原酸酯似乎是反应中的中间体。

  DOI：

  10.1016/s0040-4039(00)95905-7

文献信息

• Dipolar Cycloaddition of Rhodium-Generated Carbonyl Ylides with <i>p</i>-Quinones
  作者：Michael C. Pirrung、Krishna P. Kaliappan

  DOI：10.1021/ol991300s

  日期：2000.2.1

  [reaction: see text] The dipolar cycloaddition of carbonyl ylides generated by the rhodium-catalyzed decomposition of delta- and epsilon-carbonyl-alpha-diazoketones with p-quinones leads to both C=O and C=C addition products. The product ratio is solvent- and catalyst-dependent and has been optimized to favor formation of either product. The C=C addition products of naphthoquinones are used in the

  [反应：见正文]由铑催化的对位和对位羰基-α-重氮酮与对苯醌的铑催化分解而产生的羰基内酯的偶极环加成导致C = O和C = C加成产物。产物比例取决于溶剂和催化剂，并且已经过优化以有利于两种产物的形成。萘醌的C ＝ C加成产物用于使伊柳定和蒽醌抗癌剂杂交的结构的组装。
• Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with the geometric requirements of dipole formation
  作者：Albert Padwa、Richard L. Chinn、Susan F. Hornbuckle、Zhijia J. Zhang

  DOI：10.1021/jo00010a019

  日期：1991.5

  The carbenoid intermediate derived by the treatment of several 1-diazobutanediones with rhodium(II) acetate undergoes ready transannular cyclization onto the neighboring keto group to give five-membered ring carbonyl ylides. The dipole derived from ethyl 4-diazo-2-methyl-3-oxobutyrate was found to undergo a rapid proton transfer, producing 5-ethoxy-4-methyl-3-(2H)-furanone. When the position adjacent to the diazo carbonyl group is blocked with two substituent groups, however, smooth 1,3-dipolar cycloaddition occurs. The observed regioselectivity can be nicely accommodated in terms of frontier molecular orbital (FMO) theory. A type II FMO interaction is involved since carbonyl ylides possess one of the smallest HOMO-LUMO energy gaps of common 1,3-dipoles. The rhodium(II)-catalyzed reaction of 1-diazo-6-phenyl-2,6-hexanedione afforded a mixture of products. In addition to the expected cycloadduct, a product derived from the bimolecular addition of the rhodium carbenoid to benzene was obtained. The formation of a mixture of products in this case suggests that entropic factors have sufficiently retarded the rate of intramolecular cyclization so as to allow the bimolecular reaction with benzene to occur. No observable cycloadduct was obtained from the diazohexanedione system, thereby indicating that the longer tether was sufficient to shut down dipole formation.
• MILLER R. D.; THEIS W., TETRAHEDRON LETT., 28,(1987) N 10, 1039-1042
  作者：MILLER R. D.、 THEIS W.

  DOI：——

  日期：——
• The acid catalyzed cyclization of diazoketones: Preparation of 2,4(3H,5H) furandiones
  作者：R.D Miller、W Theis

  DOI：10.1016/s0040-4039(00)95905-7

  日期：1987.1

  Diazoketones derived from substituted ethyl hydrogen malonates produced by the selective hydrolysis of the corresponding malonate esters cyclize in the presence of catalytic amounts of boron trifluoride etherate in methanol to yield 2,4(3H,5H) furandiones. The cyclic keto orthoesters appear to be intermediates in the reaction.

  通过在甲醇中催化量的三氟化硼醚化物的存在下，由相应的丙二酸酯的选择性水解产生的由取代的丙二酸氢乙酯生成的重氮酮环化，生成2,4（3H，5H）呋喃二酮。环状酮基原酸酯似乎是反应中的中间体。